EP0584921A2 - Pyrotechnic sheet material - Google Patents
Pyrotechnic sheet material Download PDFInfo
- Publication number
- EP0584921A2 EP0584921A2 EP19930305520 EP93305520A EP0584921A2 EP 0584921 A2 EP0584921 A2 EP 0584921A2 EP 19930305520 EP19930305520 EP 19930305520 EP 93305520 A EP93305520 A EP 93305520A EP 0584921 A2 EP0584921 A2 EP 0584921A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- sheet material
- pyrotechnic sheet
- oxidizable
- copolymers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/12—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones
- C06B45/14—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones a layer or zone containing an inorganic explosive or an inorganic explosive or an inorganic thermic component
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/225—Oblique incidence of vaporised material on substrate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
- Y10T428/12569—Synthetic resin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
- Y10T428/31544—Addition polymer is perhalogenated
Definitions
- This invention relates to pyrotechnic material in sheet form and to a method of manufacturing the said material.
- the material is useful in ignition systems in, for example, gas generators, rocket motors, shock wave transmission tubes, and heat generators of inflators for gas bags of vehicle occupancy safety restraint systems.
- Pyrotechnic sheet material consisting of one or more substrate layers of oxidizing polymeric film having a layer of oxidizable material on at least a portion of at least one surface of the, or each, substrate layer, the polymeric film and the oxidizable material being conjointly capable of reacting together exothermically on ignition, has been described in PCT International Publications Nos WO 90/10611 and WO 90/10724. Improved pyrotechnic sheet material having an enhanced burning rate has been described in our co-pending United Kingdom patent application No 9304763.7.
- the preferred oxidizable material of the aforedescribed pyrotechnic sheet material comprises a metal selected from the group consisting of lithium, sodium, magnesium, beryllium, calcium, strontium, barium, zirconium, and alloys comprising any one or more thereof, the most preferred metal being magnesium.
- the metal is vapour-deposited on the film by known methods, the amount of metal being preferably substantially stoichiometric at the location of the film underlying the metal.
- the layer of oxidizable material oxidizes at a slow but significant rate when stored under normal atmospheric conditions. This effectively progressively diminishes the reaction energy available from the material and would seriously reduce the storage period during which reliable performance could be guaranteed.
- a layer of magnesium as the oxidizing layer of pyrotechnic sheet material will oxidize at a rate of about 3 microns per year from the surface and if the material were used in a vehicle occupant safety restraint system, where a guaranteed storage life of up to 15 years is required, the thickness of magnesium layer required would be > 60 microns instead of 15-20 microns required for reaction with the oxidizing polymer.
- the oxidizable material can be advantageously passivated by a dense non-porous layer of metal oxide or a metal which has a dense, non-porous oxide, thereby significantly increasing the storage life of the pyrotechnic sheet material.
- a pyrotechnic sheet material comprises a substrate of oxidizing polymeric film; a layer of oxidizable material on at least a portion of at least one surface thereof, the substrate and the oxidizable material being conjointly capable of reacting together exothermically on ignition; and a protective barrier layer of passivating material overlying the said oxidizable material, said passivating material comprising a passive metal or an oxide of a passive metal.
- a passive metal is a metal on which is readily formed a dense oxide layer that prevents further oxidization of the metal.
- suitable passive metals include titanium, aluminium, silicon, chromium, nickel, tin, indium, zinc, copper and alloys comprising any one or more thereof.
- Passive metals may be deposited as a layer on the surface of the oxidizable material by vapour deposition at low pressure either by direct evaporation or by magnetron sputtering, the latter being preferred.
- Oxides of passive metals may be deposited either by direct magnetron sputtering or formed during metal sputtering.
- metals or oxides may be deposited by magnetron sputtering or from a vapour of a passive metal compound which decomposes or oxidizes to form a passive metal or passive metal oxide.
- Coating of films by high vacuum vapour-deposition are well known in the art of web coating and have been described in the book "Web Processing and Converting Technology” (Van Nostrand Reinhold Company) - chapter entitled “High Vacuum Roll Coating” by Ernst K Harwig. It is generally preferable to deposit a layer of passive metal on the oxidizable material and to allow the passive metal to form a protective dense oxide layer on its surface in storage. Pyrotechnic sheet material having such a protective barrier layer can be stored without significant oxidization of the reactive oxidizable material. The useful life of devices containing the pyrotechnic sheet can thereby be significantly extended.
- the deposited layer of passivating material may conveniently and effectively be from 2 to 200 nanometres, preferably 5 to 60 nanometres thick.
- the substrate of oxidizing polymeric film is coated on both sides with oxidizable material but in some cases, for example to facilitate heat sealing of thermoplastic film, portions of the film may be left uncoated.
- a particularly preferred oxidizing polymeric film is that used in the pyrotechnic sheet material described in PCT International Publications Nos. WO 90/10611 and WO 90/10724.
- the oxidizing polymeric film described therein contains atoms chemically bound therein selected from the group consisting of halogens (especially fluorine), oxygen, sulphur, nitrogen and phosphorous.
- Preferred films comprise fluoropolymer such as polytetrafluoroethylene (PTFE) but other suitable polymeric films include those comprising polychlorotrifluoroethylene, polyhexafluoropropylene, copolymers of trifluoroethylene and hexafluoropropylene either with each other or with tetrafluoroethylene, copolymers of hexafluoropropylene and vinylidene fluoride, copolymers of tetrafluoroethylene and perfluoropropylene, copolymers of chlorotrifluoroethylene and vinylidene fluoride, homopolymers of perfluoropropylene, copolymers of perfluoropropylene and vinylidene fluoride, trichloroethylene homopolymers, copolymers of trichloroethylene and vinylidene fluoride, mixtures of two or more such polymers or mixtures of any one or more of such polymers with PTFE.
- PTFE
- the preferred oxidizable material comprises the aforementioned metals used in the pyrotechnic sheet material described in PCT International Publications Nos WO 90/10611 and WO 90/10724.
- the preferred metal is magnesium or an alloy thereof.
- the ratio of metal to the substrate polymer film is preferably substantially stoichiometric at the location of the film underlying the metal.
- the ignition reaction of a typical pyrotechnic sheet consisting of PTFE and magnesium on ignition can be expressed by the equation 2(C2F4)n + 2nMg -> 2nMgF2(g) + 2nC (s) + 5.98MJ/kg.
- the amount of material in the passivating layer will generally be too small to have any significant effect on the reaction and, in particular, it will not give rise to any toxic products which could affect any occupant in a vehicle having a safety restraint system containing the pyrotechnic sheet material.
- the rate of energy release on ignition varies inversely with the thickness of the pyrotechnic sheet material and, accordingly, the thickness will be chosen to attain desired energy release.
- the polymeric film will generally have a thickness of 6 to 60 microns, typically 10-50 microns and the total thickness of the oxidizable metal layer or layers will have the thickness of 2 to 30 microns, typically 10 to 15 microns.
- the pyrotechnic sheet material of the invention may be used in any convenient shape or configuration, for example, in flat sheets, strips, tapes or discs, or it may be folded, wrapped, wrinkled, pleated, corrugated, fluted or wrapped around a former such as a rod or tube.
- the sheet may be provided with spacer elements, for example protrusions formed on the surface, as described in our co-pending United Kingdom Patent Application No 9304763.7.
- spacer elements are effective to prevent intimate contact of adjacent surfaces for example of overlying sheets and thus facilitate rapid combustion of the pyrotechnic material by allowing hot gas and flame to travel ahead of the burning face and initiate the material at downstream positions.
- the invention also includes a method of manufacturing a pyrotechnic sheet material which comprises depositing a layer of oxidizable material on at least a portion of at least one surface of oxidizing polymeric film, the polymeric film and the oxidizable material being conjointly capable of reacting together exothermically on ignition, and depositing on the oxidizable material an overlying layer of passivating material comprising a passive metal or an oxide of a passive metal.
- the oxidizable material is vapour-deposited at low pressure on a polymer substrate by direct evaporation or magnetron sputtering.
- the passivating material is preferably vapour-deposited on the oxidizable material by direct evaporation or by magnetron sputtering of a passive metal, or a passive metal compound which decomposes or oxidizes to form a passive metal or passive metal oxide, or by magnetron sputtering of a passive metal oxide.
- pyrotechnic sheet material designated generally by the number 10 consists of a substrate 11 of oxidizing polymeric film, for example of polychlorotrifluoroethylene, coated on each side with a vapour-deposited layer of oxidizable metal for example magnesium 12. Each layer of oxidizable metal is coated with a vapour-deposited layer of passive metal 13.
- a pyrotechnic sheet material was prepared by vapour-depositing a 10 micron thick layer of magnesium evenly on each side of a 20 micron thick substrate of polytetrafluoroethylene (PTFE) film, the total magnesium amouning to 60% of the substrate. Each magnesium layer was then overlaid with a 10 nanometer thick coating of aluminium.
- PTFE polytetrafluoroethylene
- magnesium was vapour-deposited onto the substrate polymeric film by direct evaporation at high vacuum and the aluminium was subsequently deposited on the magnesium by magnetron sputtering wherein an ionised stream of Argon gas at low pressure was accelerated onto an aluminium cathode in a magnetic field to eject aluminium atoms or particles at high energy which were deposited on the magnesium surface.
- the pyrotechnic sheet material was exposed for 9 weeks in air at 20°C and 90% relative humidity and analysed by electron spectroscopy chemical analysis (ESCA). It was found that hard aluminium oxide had formed to a depth of 3.6 nanometers below the exposed surface of the aluminium providing a protective layer on the sheet material. In comparison a similar pyrotechnic sheet material without the aluminium coating lost almost all its magnesium coating after exposure for the same period in the same moist atmospheric conditions, the magnesium becoming oxidised and falling away from the substrate.
- ESA electron spectroscopy chemical analysis
- a pyrotechnic sheet material was prepared as described in Example 1 except that the substrate was polychlorotrifluoroethylene and the passive metal coating of aluminium was replaced by a 30 nanometer thick layer of titanium deposited by magnetron sputtering.
- a pyrotechnic sheet material was prepared as described in Example 1 except that the coating of aluminium was vapour-deposited on the magnesium by direct evaporation at low pressure.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
Description
- This invention relates to pyrotechnic material in sheet form and to a method of manufacturing the said material. The material is useful in ignition systems in, for example, gas generators, rocket motors, shock wave transmission tubes, and heat generators of inflators for gas bags of vehicle occupancy safety restraint systems.
- Pyrotechnic sheet material consisting of one or more substrate layers of oxidizing polymeric film having a layer of oxidizable material on at least a portion of at least one surface of the, or each, substrate layer, the polymeric film and the oxidizable material being conjointly capable of reacting together exothermically on ignition, has been described in PCT International Publications Nos WO 90/10611 and WO 90/10724. Improved pyrotechnic sheet material having an enhanced burning rate has been described in our co-pending United Kingdom patent application No 9304763.7.
- The use of the aforesaid pyrotechnic sheet material to ignite a propellant charge has been described in our co-pending European patent application no 92300835-3 and hybrid inflators containing gas heating elements comprising the pyrotechnic sheet material have been described in our co-pending United Kingdom patent application no 9302503.9.
- The preferred oxidizable material of the aforedescribed pyrotechnic sheet material comprises a metal selected from the group consisting of lithium, sodium, magnesium, beryllium, calcium, strontium, barium, zirconium, and alloys comprising any one or more thereof, the most preferred metal being magnesium. Advantageously the metal is vapour-deposited on the film by known methods, the amount of metal being preferably substantially stoichiometric at the location of the film underlying the metal.
- We have found that in the aforedescribed pyrotechnic sheet material the layer of oxidizable material oxidizes at a slow but significant rate when stored under normal atmospheric conditions. This effectively progressively diminishes the reaction energy available from the material and would seriously reduce the storage period during which reliable performance could be guaranteed. Thus a layer of magnesium as the oxidizing layer of pyrotechnic sheet material will oxidize at a rate of about 3 microns per year from the surface and if the material were used in a vehicle occupant safety restraint system, where a guaranteed storage life of up to 15 years is required, the thickness of magnesium layer required would be > 60 microns instead of 15-20 microns required for reaction with the oxidizing polymer. We have further found that the oxidizable material can be advantageously passivated by a dense non-porous layer of metal oxide or a metal which has a dense, non-porous oxide, thereby significantly increasing the storage life of the pyrotechnic sheet material.
- In accordance with the present invention a pyrotechnic sheet material comprises a substrate of oxidizing polymeric film; a layer of oxidizable material on at least a portion of at least one surface thereof, the substrate and the oxidizable material being conjointly capable of reacting together exothermically on ignition; and a protective barrier layer of passivating material overlying the said oxidizable material, said passivating material comprising a passive metal or an oxide of a passive metal.
- In this context a passive metal is a metal on which is readily formed a dense oxide layer that prevents further oxidization of the metal. Examples of suitable passive metals include titanium, aluminium, silicon, chromium, nickel, tin, indium, zinc, copper and alloys comprising any one or more thereof.
- Passive metals may be deposited as a layer on the surface of the oxidizable material by vapour deposition at low pressure either by direct evaporation or by magnetron sputtering, the latter being preferred. Oxides of passive metals may be deposited either by direct magnetron sputtering or formed during metal sputtering. Alternatively, metals or oxides may be deposited by magnetron sputtering or from a vapour of a passive metal compound which decomposes or oxidizes to form a passive metal or passive metal oxide. Coating of films by high vacuum vapour-deposition (including magnetron sputtering) are well known in the art of web coating and have been described in the book "Web Processing and Converting Technology" (Van Nostrand Reinhold Company) - chapter entitled "High Vacuum Roll Coating" by Ernst K Harwig. It is generally preferable to deposit a layer of passive metal on the oxidizable material and to allow the passive metal to form a protective dense oxide layer on its surface in storage. Pyrotechnic sheet material having such a protective barrier layer can be stored without significant oxidization of the reactive oxidizable material. The useful life of devices containing the pyrotechnic sheet can thereby be significantly extended.
- The deposited layer of passivating material may conveniently and effectively be from 2 to 200 nanometres, preferably 5 to 60 nanometres thick.
- Preferably the substrate of oxidizing polymeric film is coated on both sides with oxidizable material but in some cases, for example to facilitate heat sealing of thermoplastic film, portions of the film may be left uncoated.
- A particularly preferred oxidizing polymeric film is that used in the pyrotechnic sheet material described in PCT International Publications Nos. WO 90/10611 and WO 90/10724. The oxidizing polymeric film described therein contains atoms chemically bound therein selected from the group consisting of halogens (especially fluorine), oxygen, sulphur, nitrogen and phosphorous. Preferred films comprise fluoropolymer such as polytetrafluoroethylene (PTFE) but other suitable polymeric films include those comprising polychlorotrifluoroethylene, polyhexafluoropropylene, copolymers of trifluoroethylene and hexafluoropropylene either with each other or with tetrafluoroethylene, copolymers of hexafluoropropylene and vinylidene fluoride, copolymers of tetrafluoroethylene and perfluoropropylene, copolymers of chlorotrifluoroethylene and vinylidene fluoride, homopolymers of perfluoropropylene, copolymers of perfluoropropylene and vinylidene fluoride, trichloroethylene homopolymers, copolymers of trichloroethylene and vinylidene fluoride, mixtures of two or more such polymers or mixtures of any one or more of such polymers with PTFE.
- The preferred oxidizable material comprises the aforementioned metals used in the pyrotechnic sheet material described in PCT International Publications Nos WO 90/10611 and WO 90/10724. The preferred metal is magnesium or an alloy thereof. The ratio of metal to the substrate polymer film is preferably substantially stoichiometric at the location of the film underlying the metal. The ignition reaction of a typical pyrotechnic sheet consisting of PTFE and magnesium on ignition can be expressed by the equation
The amount of material in the passivating layer will generally be too small to have any significant effect on the reaction and, in particular, it will not give rise to any toxic products which could affect any occupant in a vehicle having a safety restraint system containing the pyrotechnic sheet material. - The rate of energy release on ignition varies inversely with the thickness of the pyrotechnic sheet material and, accordingly, the thickness will be chosen to attain desired energy release. Thus the polymeric film will generally have a thickness of 6 to 60 microns, typically 10-50 microns and the total thickness of the oxidizable metal layer or layers will have the thickness of 2 to 30 microns, typically 10 to 15 microns.
- The pyrotechnic sheet material of the invention may be used in any convenient shape or configuration, for example, in flat sheets, strips, tapes or discs, or it may be folded, wrapped, wrinkled, pleated, corrugated, fluted or wrapped around a former such as a rod or tube.
- If desired, for enhanced rate and violence of burning, the sheet may be provided with spacer elements, for example protrusions formed on the surface, as described in our co-pending United Kingdom Patent Application No 9304763.7. These spacer elements are effective to prevent intimate contact of adjacent surfaces for example of overlying sheets and thus facilitate rapid combustion of the pyrotechnic material by allowing hot gas and flame to travel ahead of the burning face and initiate the material at downstream positions.
- The invention also includes a method of manufacturing a pyrotechnic sheet material which comprises depositing a layer of oxidizable material on at least a portion of at least one surface of oxidizing polymeric film, the polymeric film and the oxidizable material being conjointly capable of reacting together exothermically on ignition, and depositing on the oxidizable material an overlying layer of passivating material comprising a passive metal or an oxide of a passive metal.
- Preferably the oxidizable material is vapour-deposited at low pressure on a polymer substrate by direct evaporation or magnetron sputtering. The passivating material is preferably vapour-deposited on the oxidizable material by direct evaporation or by magnetron sputtering of a passive metal, or a passive metal compound which decomposes or oxidizes to form a passive metal or passive metal oxide, or by magnetron sputtering of a passive metal oxide.
- The invention is further described by way of example only with reference to the accompanying drawing which is a diagrammatic perspective, part-sectional view of the pyrotechnic sheet material of the invention.
- Referring to the drawing, pyrotechnic sheet material designated generally by the
number 10 consists of asubstrate 11 of oxidizing polymeric film, for example of polychlorotrifluoroethylene, coated on each side with a vapour-deposited layer of oxidizable metal forexample magnesium 12. Each layer of oxidizable metal is coated with a vapour-deposited layer ofpassive metal 13. - Embodiments of the invention are further described in the following Examples.
- A pyrotechnic sheet material was prepared by vapour-depositing a 10 micron thick layer of magnesium evenly on each side of a 20 micron thick substrate of polytetrafluoroethylene (PTFE) film, the total magnesium amouning to 60% of the substrate. Each magnesium layer was then overlaid with a 10 nanometer thick coating of aluminium.
- In the preparation of the sheet material magnesium was vapour-deposited onto the substrate polymeric film by direct evaporation at high vacuum and the aluminium was subsequently deposited on the magnesium by magnetron sputtering wherein an ionised stream of Argon gas at low pressure was accelerated onto an aluminium cathode in a magnetic field to eject aluminium atoms or particles at high energy which were deposited on the magnesium surface.
- The pyrotechnic sheet material was exposed for 9 weeks in air at 20°C and 90% relative humidity and analysed by electron spectroscopy chemical analysis (ESCA). It was found that hard aluminium oxide had formed to a depth of 3.6 nanometers below the exposed surface of the aluminium providing a protective layer on the sheet material. In comparison a similar pyrotechnic sheet material without the aluminium coating lost almost all its magnesium coating after exposure for the same period in the same moist atmospheric conditions, the magnesium becoming oxidised and falling away from the substrate.
- A pyrotechnic sheet material was prepared as described in Example 1 except that the substrate was polychlorotrifluoroethylene and the passive metal coating of aluminium was replaced by a 30 nanometer thick layer of titanium deposited by magnetron sputtering.
- A pyrotechnic sheet material was prepared as described in Example 1 except that the coating of aluminium was vapour-deposited on the magnesium by direct evaporation at low pressure.
Claims (10)
- A pyrotechnic sheet material(10) comprising a substrate(11) of oxidizing polymeric film; a layer of oxidizable material(12) on at least a portion of at least one surface thereof, the polymeric film and the oxidizable material being conjointly capable of reacting together exothermically on ignition; characterised by having a protective barrier layer of passivating material overlying the said oxidizing material, said passivating material comprising a passive metal(13) (as defined herein) or an oxide of a passive metal.
- A pyrotechnic sheet material as claimed in claim 1 characterised in that the layer of passivating material(13) is a vapour-deposited layer.
- A pyrotechnic sheet material as claimed in claim 1 or claim 2 characterised in that the layer of passivating material(13) is from 2 to 200 nanometres thick.
- A pyrotechnic sheet material as claimed in any one of claims 1 to 3 characterised in that the substrate(11) of oxidizing polymeric film is coated on both sides with a layer of oxidizable material(12) and each layer of oxidizable material is coated with a layer of passivating material (13).
- Pyrotechnic sheet material as claimed in any one of claims 1 to 4 characterised in that the oxidizing polymeric film(11) comprises fluoropolymer selected from the group consisting of polytetrafluoroethylene, polychlorotrifluoroethylene, polyhexafluoropropylene, copolymers of trifluoroethylene and hexafluoropropylene, copolymers of trifluoroethylene and tetrafluoroethylene, copolymers of hexafluoropropylene and tetrafluoroethylene, copolymers of hexafluoropropylene and vinylidene fluoride, copolymers of tetrafluoroethylene and perfluoropropylene, copolymers of chlorotrifluoroethylene and vinylidene fluoride, homopolymers of perfluoropropylene, copolymers of perfluoropropylene and vinylidene fluoride, trichloroethylene homopolymers, copolymers of trichloroethylene and vinylidene fluoride and mixtures of two or more such polymers;
the oxidizable material(12) comprises a metal selected from the group consisting of lithium, sodium, magnesium, beryllium, calcium, strontium, barium, zirconium, and alloys comprising any one or more thereof vapour-deposited on the polymeric film; and the passive metal (13) comprises vapour-deposited metal selected from the group consisting of titanium, aluminium, silicon, chromium, nickel, tin, indium, zinc, copper and alloys comprising of any one or more thereof. - Pyrotechnic sheet material as claimed in claim 5 comprising a substrate film(11) of oxidizing polymr 6 to 60 microns thick having vapour-deposited on each side a layer of magnesium(12) 2 to 30 microns thick, characterised by having a vapour-deposited layer of passivating material (13) 5 to 60 nanometers thick overlying the magnesium layer.
- A method of manufacturing a pyrotechnic sheet material which comprises depositing a layer of oxidizable material(12) on at least a portion of at least one surface of oxidizing polymeric film(11), the polymeric film and the oxidizable material being cojointly capable of reacting together exothermically on ignition, characterised in that an overlying layer of passivating material (13) comprising a passive metal or an oxide of a passive metal is deposited on the oxidizable material.
- A method as claimed in claim 7 characterised in that the oxidizable material(12) and/or the layer of passivating material(13) are vapour-deposited at low pressure by direct evaporation or magnetron sputtering.
- A pyrotechnic sheet material whenever prepared by a method as claimed in claim 7 or claim 8.
- An inflator for a vehicle occupant safety restraint system comprising pyrotechnic sheet material as claimed in any one of the claims 1 to 6 and claim 9.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9216517 | 1992-08-04 | ||
GB9216517A GB9216517D0 (en) | 1992-08-04 | 1992-08-04 | Pyrotechnic sheet material |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0584921A2 true EP0584921A2 (en) | 1994-03-02 |
EP0584921A3 EP0584921A3 (en) | 1994-10-19 |
EP0584921B1 EP0584921B1 (en) | 1996-10-09 |
Family
ID=10719779
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19930305520 Expired - Lifetime EP0584921B1 (en) | 1992-08-04 | 1993-07-14 | Pyrotechnic sheet material |
Country Status (10)
Country | Link |
---|---|
US (1) | US5415932A (en) |
EP (1) | EP0584921B1 (en) |
JP (1) | JPH06172076A (en) |
KR (1) | KR940003724A (en) |
AU (1) | AU662435B2 (en) |
CA (1) | CA2101621A1 (en) |
DE (1) | DE69305295T2 (en) |
ES (1) | ES2092230T3 (en) |
GB (1) | GB9216517D0 (en) |
ZA (1) | ZA935322B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6527297B1 (en) | 2000-08-30 | 2003-03-04 | Autoliv Asp, Inc. | Inflator device ignition of gas generant |
EP1686110A3 (en) * | 2005-01-26 | 2012-06-13 | Diehl BGT Defence GmbH & Co.KG | Pyrotechnical charge and method for preparing the same |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5531844A (en) * | 1994-02-14 | 1996-07-02 | The United States Of America As Represented By The Secretary Of The Navy | Energetic compositions containing no volatile solvents |
CA2166748A1 (en) * | 1995-01-14 | 1996-07-15 | Sek Kwan Chan | Pyrotechnic ignition device |
US6133146A (en) * | 1996-05-09 | 2000-10-17 | Scb Technologies, Inc. | Semiconductor bridge device and method of making the same |
KR100576950B1 (en) * | 1997-09-08 | 2006-05-10 | 조디악 오토모티브 유에스 인크. | Distributed charge inflator system |
US7188567B1 (en) | 1999-11-12 | 2007-03-13 | Zodiac Automotive Us Inc. | Gas generation system |
US6465110B1 (en) | 2000-10-10 | 2002-10-15 | Material Sciences Corporation | Metal felt laminate structures |
DE10204895B4 (en) * | 2002-02-06 | 2004-07-29 | Diehl Munitionssysteme Gmbh & Co. Kg | Process for the production of reactive substances |
US7137341B2 (en) * | 2002-05-17 | 2006-11-21 | Zodiac Automotive Us Inc. | Distributed charge inflator system |
US7162958B2 (en) * | 2002-05-17 | 2007-01-16 | Zodiac Automotive Us Inc. | Distributed charge inflator system |
MXPA05004500A (en) * | 2002-10-29 | 2006-03-08 | Lucite Int Inc | Therapeutic compositions. |
US20040108030A1 (en) * | 2002-12-06 | 2004-06-10 | Mendenhall Ivan V. | Porous igniter coating for use in automotive airbag inflators |
US20050115650A1 (en) * | 2003-12-02 | 2005-06-02 | Mendenhall Ivan V. | Foamed igniter for use in automotive airbag inflators |
US20090266259A1 (en) * | 2008-04-24 | 2009-10-29 | Rustick Joseph M | Flat electric match |
RU2468478C1 (en) * | 2011-12-06 | 2012-11-27 | ОАО Федеральный научно-производственный центр "НИИ прикладной химии" | Pyrotechnical source of electric current |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3381473A (en) * | 1964-06-22 | 1968-05-07 | United Aircraft Corp | High energy fuel systems |
US3390026A (en) * | 1960-11-25 | 1968-06-25 | Nat Res Corp | Process of forming a protective coating on particulate material, and coated article obtained thereby |
WO1990010724A1 (en) * | 1989-03-13 | 1990-09-20 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Pyrotechnic materials |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9319886D0 (en) * | 1993-09-27 | 1993-12-15 | Ici Plc | Pyrotechnic material |
-
1992
- 1992-08-04 GB GB9216517A patent/GB9216517D0/en active Pending
-
1993
- 1993-07-14 EP EP19930305520 patent/EP0584921B1/en not_active Expired - Lifetime
- 1993-07-14 ES ES93305520T patent/ES2092230T3/en not_active Expired - Lifetime
- 1993-07-14 DE DE1993605295 patent/DE69305295T2/en not_active Expired - Fee Related
- 1993-07-22 ZA ZA935322A patent/ZA935322B/en unknown
- 1993-07-29 CA CA 2101621 patent/CA2101621A1/en not_active Abandoned
- 1993-07-29 JP JP18798993A patent/JPH06172076A/en active Pending
- 1993-08-04 KR KR1019930015103A patent/KR940003724A/en not_active IP Right Cessation
- 1993-08-04 AU AU44459/93A patent/AU662435B2/en not_active Ceased
- 1993-08-04 US US08/101,052 patent/US5415932A/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3390026A (en) * | 1960-11-25 | 1968-06-25 | Nat Res Corp | Process of forming a protective coating on particulate material, and coated article obtained thereby |
US3381473A (en) * | 1964-06-22 | 1968-05-07 | United Aircraft Corp | High energy fuel systems |
WO1990010724A1 (en) * | 1989-03-13 | 1990-09-20 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Pyrotechnic materials |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6527297B1 (en) | 2000-08-30 | 2003-03-04 | Autoliv Asp, Inc. | Inflator device ignition of gas generant |
US6666476B2 (en) | 2000-08-30 | 2003-12-23 | Autoliv Asp, Inc. | Expandable fluid inflator device with pyrotechnic coating |
US6739621B2 (en) | 2000-08-30 | 2004-05-25 | Autoliv Asp, Inc. | Inflator device ignition of gas generant |
EP1686110A3 (en) * | 2005-01-26 | 2012-06-13 | Diehl BGT Defence GmbH & Co.KG | Pyrotechnical charge and method for preparing the same |
Also Published As
Publication number | Publication date |
---|---|
EP0584921A3 (en) | 1994-10-19 |
ES2092230T3 (en) | 1996-11-16 |
US5415932A (en) | 1995-05-16 |
JPH06172076A (en) | 1994-06-21 |
ZA935322B (en) | 1994-03-11 |
CA2101621A1 (en) | 1994-02-05 |
AU662435B2 (en) | 1995-08-31 |
GB9216517D0 (en) | 1992-09-23 |
EP0584921B1 (en) | 1996-10-09 |
AU4445993A (en) | 1994-02-10 |
DE69305295D1 (en) | 1996-11-14 |
DE69305295T2 (en) | 1997-03-06 |
KR940003724A (en) | 1994-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0584921B1 (en) | Pyrotechnic sheet material | |
EP0463022B1 (en) | Pyrotechnic materials | |
AU661786B2 (en) | Pyrotechnic sheet material | |
Pesty et al. | Thermal stability of Pt films on TiO2 (110): evidence for encapsulation | |
US5334417A (en) | Method for forming a pack cementation coating on a metal surface by a coating tape | |
JPH05193437A (en) | Gas generator | |
US8465608B1 (en) | Methods for forming ignitable heterogeneous structures | |
US5721392A (en) | Pyrotechnic ignition device | |
GB2269380A (en) | Pyrotechnic sheet material | |
EP0645354B1 (en) | Pyrotechnic Material | |
WO1994018359A1 (en) | Diffusion barrier layers | |
JPH08217588A (en) | Pyrowork sheet material and its production | |
DE4015010C1 (en) | ||
GB2269379A (en) | Pyrotechnic sheet metal | |
Whitaker et al. | Atomic oxygen effects on LDEF experiment AO171 | |
JP3123371B2 (en) | Barrier laminate | |
Sanders et al. | Pinhole plugging characteristics of silica/iron/silver protective coatings in atomic oxygen environments | |
NO175586B (en) | Pyrotechnic material, pyrotechnic delay element and pyrotechnic element | |
Guesdon | Coated strip and a fabrication process for that strip | |
JPH07256813A (en) | Laminate | |
Folger et al. | Rolling of Sensitive Target Foils Being Coated with Evaporated Metal Layers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE ES FR GB IT SE |
|
17P | Request for examination filed |
Effective date: 19940701 |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE ES FR GB IT SE |
|
17Q | First examination report despatched |
Effective date: 19950309 |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
RBV | Designated contracting states (corrected) |
Designated state(s): BE DE ES FR IT SE |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES FR IT SE |
|
REF | Corresponds to: |
Ref document number: 69305295 Country of ref document: DE Date of ref document: 19961114 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2092230 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19970613 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19970617 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19970618 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19970623 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19970715 Year of fee payment: 5 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980715 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980715 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980731 |
|
BERE | Be: lapsed |
Owner name: IMPERIAL CHEMICAL INDUSTRIES P.L.C. Effective date: 19980731 |
|
EUG | Se: european patent has lapsed |
Ref document number: 93305520.4 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990331 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990501 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 19990811 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050714 |